Manufacturing method for deposition mask, metal plate used for producing deposition mask, and manufacturing method for said metal sheet

ABSTRACT

The present invention provides a metal sheet, on a first surface of which a resist pattern having a narrow width can be stably provided. This manufacturing method for a metal sheet includes a preparation step of preparing a sheet material comprising an iron alloy that contains nickel. When a composition analysis of the first surface of the metal sheet obtained from the sheet material is performed using X-ray photoelectron spectroscopy, the ratio A1/A2 obtained by the result of the X-ray photoelectron spectroscopy does not exceed 0.4, where A1 is the sum of the peak area value of nickel oxide and the peak area value of nickel hydroxide, and A2 is the sum of the peak area value of iron oxide and the peak area value of iron hydroxide.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 15/548,897,filed Aug. 4, 2017, which in turn is the National Stage of InternationalApplication No. PCT/JP2016/053580, filed Feb. 5, 2016, which designatedthe United States, the entireties of which are incorporated herein byreference.

FIELD OF THE INVENTION

The present invention relates to a manufacturing method for a depositionmask with a plurality of through-holes formed therein. In addition, thepresent invention relates to a method for manufacturing a metal used forproducing the deposition mask, and a manufacturing method for the metalsheet.

BACKGROUND OF THE INVENTION

A display device used in a portable device such as a smart phone and atablet PC is required to have high fineness, e.g., a pixel density of300 ppi or more. In addition, there is increasing demand that theportable device is applicable in the full high-definitions reference. Inthis case, the pixel density of the display device needs to be 450 ppior more, for example.

An organic EL display device draws attention because of its excellentresponsibility and low power consumption. A known method for formingpixels of an organic EL display device is a method which uses adeposition mask including through-holes that are arranged in a desiredpattern, and forms pixels in the desired pattern. To be specific, adeposition mask is firstly brought into tight contact with a substratefor organic EL display device, and then the substrate and the depositionmask in tight contact therewith are put into a deposition apparatus soas to deposit an organic material and so on.

A deposition mask can be generally manufactured by forming through-holesin a metal plate by etching using photolithographic technique (see, forexample, Patent Document 1). For example, a first resist pattern isfirstly formed on a first surface of the metal plate, and a secondresist pattern is formed on a second surface of the metal plate. Then,an area of the second surface of the metal plate, which is not coveredwith the second resist pattern, is etched to form second recesses in thesecond surface of the metal plate. Thereafter, an area of the firstsurface of the metal plate, which is not covered with the first resistpattern, is etched to form first recesses in the first surface of themetal plate. At this time, by etching the areas such that each firstrecess and each second recess communicate with each other, through-holespassing through the metal plate can be formed.

In a deposition step using a deposition mask, a deposition mask and asubstrate are arranged such that a second surface side of the depositionmask faces the substrate. In addition, a crucible storing a depositionmaterial such as an organic material is arranged on a first surface sideof the deposition mask. Then, the deposition material is heated toevaporate or sublimate the deposition material. The evaporated orsublimated deposition material adheres to the substrate through thethrough-holes in the deposition mask. As a result, the depositionmaterial is deposited on a surface of the substrate, in a desiredpattern corresponding to the through-hole positions of the depositionmask.

-   Patent Document 1: 3132014-148740A

SUMMARY OF THE INVENTION

As a pixel density of an organic EL display device increases, a size andan arrangement pitch of through-holes of a deposition mask decrease.When through-holes are formed in a metal plate by etching using thephotolithographic technique, a width of resist pattern provided on afirst surface or a second surface of the metal plate narrows. Thus, itis required for a resist film for forming a resist pattern to have ahigh resolution. To make narrower the resist pattern width means that acontact area between the resist pattern and the metal plate is reduced.Thus, it is also required for the resist film for forming a resistpattern to have a high adhesion force to the metal plate.

The present invention has been made in view of the above circumstances.The object of the present invention is to provide a method formanufacturing a metal plate on which surface a resist pattern of anarrow width can be stably provided, and such a metal plate. Inaddition, the present invention relates to a method for manufacturing adeposition mask using such a metal plate.

The present invention is a manufacturing method for a metal plate usedfor manufacturing a deposition mask having a plurality of through-holesformed therein, the method comprising a preparation step of preparing aplate member made of an iron alloy containing nickel, wherein: when acomposition analysis of a first surface of the metal plate obtained fromthe plate member is performed by using an X-ray photoelectronspectroscopy, a ratio A1/A2 obtained by the result of the X-rayphotoelectron spectroscopy is 0.4 or less, where A1 is a sum of a peakplanar dimension value of nickel oxide and a peak planar dimension valueof nickel hydroxide, and A2 is a sum of a peak planar dimension value ofiron oxide and a peak planar dimension value of iron hydroxide; and inthe composition analysis of the first surface of the metal plate bymeans of the X-ray photoelectron spectroscopy, an incident angle of anX-ray emitted to the metal plate on the first surface is 45 degrees, andan acceptance angle of photoelectrons discharged from the metal plate is90 degrees.

The manufacturing method for a metal plate according to the presentinvention may further comprise an annealing step of annealing the platemember to obtain the metal plate.

In the manufacturing method for a metal plate according to the presentinvention, the annealing step may be performed in an inert gasatmosphere.

In the manufacturing method for a metal plate according to the presentinvention, the preparation step may include a rolling step of rolling abase metal made of an iron alloy containing nickel.

In the manufacturing method for a metal plate according to the presentinvention, the preparation step may include a foil creating step ofcreating a plating film by using a plating liquid including a solutioncontaining a nickel compound and a solution containing an iron compound.

In the manufacturing method for a metal plate according to the presentinvention, a thickness of the metal plate may be 85 μm or less.

In the manufacturing method for a metal plate according to the presentinvention, the metal plate may be for manufacturing the deposition maskby exposing and developing a dry film attached to the first surface ofthe metal plate to form a first resist pattern, and by etching an areaof the first surface of the metal plate, the area being not covered withthe first resist pattern.

The present invention is a metal plate used for manufacturing adeposition mask having a plurality of through-holes formed therein,wherein: when a composition analysis of a first surface of the metalplate is performed by using an X-ray photoelectron spectroscopy, a ratioA1/A2 obtained by the result of the X-ray photoelectron spectroscopy is0.4 or less, where A1 is a sum of a peak planar dimension value ofnickel oxide and a peak planar dimension value of nickel hydroxide, andA2 is a sum of a peak planar dimension value of iron oxide and a peakplanar dimension value of iron hydroxide; and in the compositionanalysis of the first surface of the metal plate by means of the X-rayphotoelectron spectroscopy, an incident angle of an X-ray emitted to themetal plate on the first surface is 45 degrees, and an acceptance angleof photoelectrons discharged from the metal plate is 90 degrees.

In the metal plate according to the present invention, a thickness ofthe metal plate may be 85 μm or less.

In the metal plate according to the present invention, the metal platemay be for manufacturing the deposition mask by exposing and developinga dry film attached to the first surface of the metal plate to form afirst resist pattern, and by etching an area of the first surface of themetal plate, the area being not covered with the first resist pattern.

The present invention is a manufacturing method for a deposition maskhaving a plurality of through-holes formed therein, the methodcomprising: a step of preparing a metal plate; a first resist patternforming step of forming a first resist pattern on a first surface of themetal plate; and an etching step of etching an area of the first surfaceof the meal plate, the area being not covered with the resist pattern,so that first recesses to define the through-holes are formed in thefirst surface of the metal plate; wherein: when a composition analysisof a first surface of the metal plate is performed by using an X-rayphotoelectron spectroscopy, a ratio A1/A2 obtained by the result of theX-ray photoelectron spectroscopy is 0.4 or less, where A1 is a sum of apeak planar dimension value of nickel oxide and a peak planar dimensionvalue of nickel hydroxide, and A2 is a sum of a peak planar dimensionvalue of iron oxide and a peak planar dimension value of iron hydroxide;and in the composition analysis of the first surface of the metal plateby means of the X-ray photoelectron spectroscopy, an incident angle ofan X-ray emitted to the metal plate on the first surface is 45 degrees,and an acceptance angle of photoelectrons discharged from the metalplate is 90 degrees.

In the manufacturing method for a deposition mask according to thepresent invention, a thickness of the metal plate may be 85 μm or less.

In the manufacturing method for a deposition mask according to thepresent invention, the first resist pattern forming step may include astep of attaching a dry film to the first surface of the metal plate,and a step of exposing and developing the dry film to form the firstresist pattern.

The present invention is a deposition mask comprising: a metal plateincluding a first surface and a second surface located oppositely to thefirst surface; and a plurality of through-holes formed in the metalplate so as to pass through from the first surface of the metal plate tothe second surface thereof; wherein: the each through-hole has a secondrecess formed in the second surface of the metal plate and a firstrecess formed in the first surface of the metal plate so as to connectto the second recess; when a composition analysis of the first surfacethe metal plate is performed by using the X-ray photoelectronspectroscopy, a ratio A1/A2 obtained by the result of the X-rayphotoelectron spectroscopy is 0.4 or less, where A1 is a sum of a peakplanar dimension value of nickel oxide and a peak planar dimension valueof nickel hydroxide, and A2 is a sum of a peak planar dimension value ofiron oxide and a peak planar dimension value of iron hydroxide; and inthe composition analysis of the first surface of the metal plate bymeans of the X-ray photoelectron spectroscopy, an incident angle of anX-ray emitted to the metal plate on the first surface is 45 degrees, andan acceptance angle of photoelectrons discharged from the metal plate is90 degrees.

In the deposition mask according to the present invention, a thicknessof the metal plate may be 85 μm or less.

According to the present invention, a resist pattern of a narrow widthcan be stably provided on a surface of a metal plate. Thus, a depositionmask for producing an organic EL display device having a high pixeldensity can be stably obtained.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view for explaining an embodiment of the present invention,which is a schematic plan view showing an example of a deposition maskapparatus including a deposition mask.

FIG. 2 is a view for explaining a deposition method by using thedeposition mask apparatus shown in FIG. 1.

FIG. 3 is a partial plan view showing the deposition mask shown in FIG.1.

FIG. 4 is a sectional view along the IV-IV line of FIG. 3.

FIG. 5 is a sectional view along the V-V line of FIG. 3.

FIG. 6 is a sectional view showing VI-VI line of FIG. 3.

FIG. 7 is an enlarged sectional view showing the through-hole shown inFIG. 4 and an area near thereto.

FIGS. 8(a) to 8(c) are views schematically showing a manufacturingmethod for a deposition mask.

FIG. 9(a) is a view showing a step of obtaining a metal plate having adesired thickness by rolling a base metal.

FIG. 9(b) is a view showing a step of annealing the metal plate obtainedby rolling.

FIG. 10 is a view showing that a composition analysis of a first surfaceof the metal plate is performed by using an X-ray photoelectronspectroscopy.

FIG. 11 is a schematic view for generally explaining an example of amanufacturing method for the deposition mask shown in FIG. 1.

FIG. 12 is a view for explaining an example of the manufacturing methodfor the deposition mask, which is a sectional view showing a step offorming a resist film on the metal plate.

FIG. 13 is a view for explaining an example of the manufacturing methodfor the deposition mask, which is a sectional view showing a step ofbringing an exposure mask into tight contact with the resist film.

FIG. 14A is a view for explaining an example of the manufacturing methodfor the deposition mask, showing an elongated metal plate in a sectionalong a normal direction.

FIG. 14B is a partial plan view when the elongated metal plate shown inFIG. 14A is seen from a first surface side.

FIG. 15 is a view for explaining an example of the manufacturing methodfor the deposition mask, showing an elongated metal plate in a sectionalong a normal direction.

FIG. 16 is a view for explaining an example of the manufacturing methodfor the deposition mask, showing an elongated metal plate in a sectionalong a normal direction.

FIG. 17 is a view for explaining an example of the manufacturing methodfor the deposition mask, showing an elongated metal plate in a sectionalong a normal direction.

FIG. 18 is a view for explaining an example of the manufacturing methodfor the deposition mask, showing an elongated metal plate in a sectionalong a normal direction.

FIG. 19 is a view for explaining an example of the manufacturing methodfor the deposition mask, showing an elongated metal plate in a sectionalong a normal direction.

FIG. 20 is a view showing a modification example of the deposition maskapparatus including a deposition mask.

FIGS. 21(a) and 21(b) are views showing a result of analyzing a firstspecimen cut out from a first winding body by using an XPS apparatus.

FIG. 22(a) is a view showing a result of analyzing nickel oxide,prepared as a first reference specimen, by using an XPS method.

FIG. 22(b) is a view showing a result of analyzing nickel hydroxide,prepared as a second reference specimen, by using the XPS method.

FIG. 23 is a view showing a resist pattern formed on a surface of afirst sample.

FIGS. 24(a) and 24(b) are views each showing a result of analyzing asecond specimen cut out from a second winding body, by using an XPSapparatus.

FIGS. 25(a) and 25(b) are views each showing a result of analyzing athird specimen cut out from a third winding body, by using the XPSapparatus.

FIGS. 26(a) and 26(b) are views each showing a result of analyzing afourth specimen cut out from a fourth winding body, by using the XPSapparatus.

FIG. 27A is a view showing a step of calculating a background line of aniron total peak on iron 2P_(3/2) orbit.

FIG. 27B is a view showing a step of separating a peak on iron alonefrom the iron total peak.

FIG. 27C is a view showing a step of calculating a peak area on ironalone.

FIG. 27D is a view showing as a reference a result of separating peakson iron oxide and iron hydroxide.

FIG. 28A is a view showing a step of calculating a background line of atotal peak on nickel 2P_(3/2) orbit.

FIG. 28B is a view showing a step of separating a peak on nickel alonefrom the nickel total peak.

FIG. 28C is a view showing a step of calculating a peak area on nickelalone.

FIG. 28D is a view showing as a reference a result of separating peakson nickel oxide and nickel hydroxide.

FIG. 29 is a view showing an example in which a part of resist patternpeels off from a metal plate in a developing solution.

DETAILED DESCRIPTION OF THE INVENTION

An embodiment of the present invention will be described herebelow withreference to the drawings. In the drawings attached to thespecification, a scale dimension, an aspect ratio and so on are changedand exaggerated from the actual ones, for the convenience of easiness inillustration and understanding.

FIGS. 1 to 20 are views for explaining an embodiment of the presentinvention and its modification example. In the below embodiment and themodification example, a manufacturing method for a deposition mask forused in patterning an organic material in a desired pattern on asubstrate, when an organic EL display apparatus is manufacture, forexample. However, not limited thereto, the present invention can beapplied to a manufacturing method for a deposition mask for varioususes.

In this specification, the terms “plate”, “sheet” and “film” are notdifferentiated from one another based only on the difference of terms.For example, the “plate” is a concept including a member that can bereferred to as sheet or film. Thus, for example, “metal plate” is notdifferentiated from a member that is referred to as “metal sheet” or“metal film” based only on the difference of terms.

In addition, the term “plate plane (sheet plane, film plane)” means aplane corresponding to a plane direction of a plate-like (sheet-like,film-like) member as a target, when the plate-like (sheet-like,film-like) member as a target is seen as a whole in general. A normaldirection used to the plate-like (sheet-like, film-like) member means anormal direction with respect to a plate plane (sheet surface, filmsurface) of the member.

Further, in this specification, terms specifying shapes, geometricconditions and their degrees, e.g., “parallel”, “perpendicular”, “same”,“similar” etc., are not limited to their strict definitions, butconstrued to include a range capable of exerting a similar function.

Deposition Mask Apparatus

Firstly, an example of a deposition mask apparatus including depositionmasks to be manufactured is described with reference mainly to FIGS. 1to 6. FIG. 1 a plan view showing an example of the deposition maskapparatus including the deposition masks. FIG. 2 is a view forexplaining a method for using the deposition mask apparatus shown inFIG. 1. FIG. 3 is a plan view showing the deposition mask seen from afirst surface side. FIGS. 4 to 6 are sectional views seen fromrespective positions of FIG. 3.

The deposition mask apparatus 10 shown in FIGS. 1 and 2 includes aplurality of deposition masks 20 each of which is formed of a metalplate 21 of substantially a rectangular shape, and a frame 15 attachedto peripheries of the deposition masks 20. Each deposition mask 20 has anumber of through-holes 25 which are formed by etching the metal plate21, which has a first surface 21 a and a second surface 21 b locatedoppositely to the first surface 21 a, from both sides of the firstsurface 21 a and the second surface 21 b. As shown in FIG. 2, thedeposition mask apparatus 10 is used for depositing a depositionmaterial to a substrate. The deposition mask apparatus 10 is supportedin a deposition apparatus 90 such that the deposition mask 20 faces alower surface of the substrate 92 such as a glass substrate, onto whichthe deposition material is to be deposited.

In the deposition apparatus 90, the deposition mask 20 and the glasssubstrate 92 are brought into tight contact with each other by amagnetic force of magnets, not shown. In the deposition apparatus 90,there are disposed below the deposition mask apparatus 10 a crucible 94storing a deposition material (e.g., organic luminescent material) 98and a heater 96 for heating the crucible 94. The deposition material 98in the crucible 94 is evaporated or sublimated by heat applied from theheater 96 so as to adhere to the surface of the substrate 92. Asdescribed above, since the deposition mask 20 has a lot of through-holes25 formed therein, the deposition material 98 adheres to the glasssubstrate 92 through the through-holes 25. As a result, a film of thedeposition material 98 is formed on the surface of the substrate 92 in adesired pattern corresponding to the positions of the through-holes 25of the deposition mask 20.

As described above, in this embodiment, the through-holes 25 arearranged in each effective area 22 in a predetermined pattern. When acolor display is desired, an organic luminescent material for red color,an organic luminescent material for green color and an organicluminescent material for blue color may be sequentially deposited, whilethe deposition mask 20 (deposition mask apparatus 10) and the glasssubstrate 92 are relatively moved little by little along the arrangementdirection of the through-holes 25 (aforementioned one direction).Alternatively, the deposition material 98 may be deposited on thesurface of the substrate 92, with the use of the deposition masks 20that differ depending on colors of the organic luminescent materials.

The frame 15 of the deposition mask apparatus 10 is attached to theperipheries of the rectangular deposition masks 20. The frame 15 isconfigured to hold each deposition mask in a taut state in order toprevent the deposition mask 20 from warping. The deposition masks 20 andthe frame 15 are fixed with respect to each other by spot welding, forexample.

The deposition process is performed inside the deposition apparatus 90in a high-temperature atmosphere. Thus, during the deposition process,the deposition masks 20, the frame 15 and the substrate 92, which areheld inside the deposition apparatus 90, are also heated. At this time,each of deposition mask 20, the frame 15 and the substrate 92 developdimensional change behaviors based on their respective thermal expansioncoefficients. In this case, when the thermal expansion coefficients ofthe deposition mask 20, the frame 15 and the substrate 92 largely differfrom one another, positioning displacement occurs because of thedifference in dimensional change. As a result, the dimensional precisionand the positional precision of the deposition material to be adhered tothe substrate 92 lower. In order to avoid this problem, the thermalexpansion coefficients of the deposition mask 20 and the frame 15 arepreferably equivalent to the thermal expansion coefficient of thesubstrate 92. For example, when a glass substrate is used as thesubstrate 92, an iron alloy containing can be used as a main material ofthe deposition mask 20 and the frame 15. For example, an iron alloycontaining 30 to 54% by mass of nickel can be used as a material of themetal plate constituting the deposition masks 20. Concrete examples ofan iron alloy containing nickel may be an invar material containing34-38% by mass of nickel, a super invar material containing cobalt inaddition to nickel, or a low thermal expansion Fe—Ni based plated alloycontaining 38 to 54% by mass of nickel. In this specification, anumerical range expressed by the symbol “-” includes numerical valuessandwiching the symbol “-”. For example, a numerical range defined bythe expression “34-38% by mass” is identical to a numerical rangedefined by an expression “not less than 34% by mass and not more than38% by mass”.

Deposition Mask

Next, the deposition mask 20 is described in detail. As shown in FIG. 1,in this embodiment, each deposition mask 20 is formed of the metal plate21, and has an outline of a substantially quadrangular shape in planview, more precisely, a substantially rectangular shape in plan view.The metal plate 21 of the deposition mask 20 includes the effective area22 in which the through-holes 25 are formed in a regular arrangement,and a peripheral area 23 surrounding the effective area 22. Theperipheral area 23 is an area for supporting the effective area 22, andis not an area through which the deposition material intended to bedeposited on the substrate passes. For example, in the deposition mask20 for use in depositing an organic luminescent material for organic ELdisplay device, the effective area 22 is an area in the deposition mask20, which faces a section on the substrate to which the organicluminescent material is deposited to form pixels, i.e., a section on thesubstrate which provides a display surface of the manufactured substratefor organic EL display device. However, for various purposes, theperipheral area 23 may have a through-hole and/or a recess. In theexample shown in FIG. 1, each effective area 22 has an outline of asubstantially quadrangular shape in plan view, more precisely, asubstantially rectangular shape in plan view.

In the illustrated example, the effective areas 22 of the depositionmask 20 are aligned, at predetermined intervals therebetween, along onedirection in parallel with a longitudinal direction of the depositionmask 20. In the illustrated example, one effective area 22 correspondsto one organic EL display device. Namely, the deposition mask apparatus10 (deposition masks 20) shown in FIG. 1 enables a multifaceteddeposition.

As shown in FIG. 3, in the illustrate example, a plurality of thethrough-holes 25 formed in each effective area 22 are arranged atpredetermined pitches along two directions perpendicular to each other.An example of the through-hole 25 formed in the metal plate 21 isdescribed in more detail with reference mainly to FIGS. 3 to 6.

As shown in FIGS. 4 to 6, a plurality of the through-holes 25 passthrough from the first surface 20 a, which is one side along a normaldirection of the deposition mask 20, to the second surface 20 b, whichis the other side among the normal direction of the deposition mask 20.In the illustrated example, as described in more detail below, firstrecesses 30 are formed in the first surface 21 a of the metal plate 21,which serves as the one side in the normal direction of the depositionmask, by an etching process, and second recesses 35 are formed in thesecond surface 21 b, which serves as the other side in the normaldirection of the metal plate 21. Each of the first recesses 30 isconnected to each of the second recesses 35, so that the second recess35 and the first recess 30 are formed to communicate with each other.Each through-hole 25 is composed of the second recess 35 and the firstrecess 30 connected to the second recess 35.

As shown in FIGS. 3 to 6, a cross-sectional area of each first recess30, in a cross section along a plate plane of the deposition mask 20 ateach position along the normal direction of the deposition mask 20,gradually decreases from the side of the first surface 20 a of thedeposition mask 20 toward the side of the second surface 20 b.Similarly, a cross-sectional area of each second recess 35, in a crosssection along the plate plane of the deposition mask 20 at each positionalong the normal direction of the deposition mask 20, graduallydecreases from the side of the second surface 20 b of the depositionmask 20 toward the side of the first surface 20 a.

As shown in FIGS. 4 to 6, a wall surface 31 of the first recess 30 and awall surface 36 of the second recess 35 are connected via acircumferential connection portion 41. The connection portion 41 isdefined by a ridge line of a bulging part where the wall surface 31 ofthe first recess 30, which inclined with respect to the normal directionof the deposition mask 20, and the wall surface 36 of the second recess35, which is inclined with respect to the normal direction of thedeposition mask 20, are merged with each other. The connection portion41 defines a through-portion 42 where an area of the through-hole 25 isminimum in plan view of the deposition mask 20.

As shown in FIGS. 4 to 6, the adjacent two through-holes 25 in the otherside surface along the normal direction of the deposition mask, i.e., inthe second surface 20 b of the deposition mask 20, are spaced from eachother along the plate plane of the deposition mask. Namely, as in thebelow-described manufacturing method, when the second recesses 35 aremade by etching the metal plate 21 from the side of the second surface21 b of the metal plate 21, which will correspond to the second surface20 b of the deposition mask 20, the second surface 21 b of the metalplate 21 remains between the two adjacent second recesses 35.

Similarly, as shown in FIGS. 4 and 6, the two adjacent first recesses 30may be spaced from each other along the plane of the deposition mask, onthe one side along the normal direction of the deposition mask, i.e., onthe side of the first surface 20 a of the deposition mask 20. Namely,the first surface 21 a of the metal plate 21 may remain between the twoadjacent first recesses 30. In the below description, a portion of theeffective area 22 of the first surface 21 a of the meal plate 21, whichis not etched and thus remains, is also referred to as top portion 43.By producing the deposition mask 20 such that such a top portion 43remains, the deposition mask 20 can have a sufficient strength. Thus, itcan be prevented that the deposition mask 20 is damaged duringtransportation, for example. However, when a width β of the top portion43 is too large, there is a possibility that shadow occurs in thedeposition step, which lowers utilization efficiency of the depositionmaterial 98. Thus, the deposition mask 20 is preferably produced suchthat the width β of the top portion 43 is excessively large. Forexample, the width β of the top portion 43 is preferably 2 μm or less.In general, the width β of the top portion 43 varies depending on adirection along which the deposition mask 20 is severed. For example,the width β of the top portion 43 shown in FIG. 4 and that of FIG. 6 maydiffer from each other. In this case, the deposition mask 30 may beformed such that the width β of the top portion 43 is 2 μm or less,regardless of a direction along which the deposition mask 20 is severed.

As shown in FIG. 5, the etching process may be performed such that twoadjacent first recesses 30 are connected to each other, depending ontheir positions. Namely, there may be a part where no first surface 21 aof the metal plate 21 remains between two adjacent first recesses 30.

As shown in FIG. 2, the deposition mask apparatus 10 is received in thedeposition apparatus 90. In this case, as shown by the two-dot chainlines in FIG. 4, the first surface 20 a of the deposition mask 20 islocated on the side of the crucible 94 holding the deposition material98, and the second surface 20 b of the deposition mask 20 faces thesubstrate 92. Thus, the deposition material 98 adheres to the substrate92 through the first recess 30 whose cross-sectional area graduallydecreases. As shown by the arrow in FIG. 4 extending from the firstsurface 20 a toward the second surface 20 b, the deposition material 98not only moves from the crucible 94 toward the substrate 92 along thenormal direction of the substrate 92, but also sometimes moves along adirection largely inclined with respect to the normal direction of thesubstrate 92. At this time, when the thickness of the deposition mask 20is large, most of the diagonally moving deposition material 98 reachesthe wall surface 31 of the first recess 30 to adhere thereto, before thedeposition material 98 passes through the through-holes 25 to reach thesubstrate 92. Thus, in order to improve a utilization efficiency of thedeposition material 98, it is considered to be preferable that thethickness t of the deposition mask 20 is reduced so that heights of thewall surface 31 of the first recess 30 and the wall surface 36 of thesecond recess 35 are reduced. Namely, it can be said that it ispreferable that a metal plate 21, which has the thickness t as small aspossible as long as the strength of the deposition mask 20 is ensured,is used as the metal plate 21 for constituting the deposition mask 20.In consideration of this point, the thickness t of the deposition mask20 in this embodiment is preferably set to be 85 μm or less, e.g.,within a range of from 5 to 85 μm. The thickness t is a thickness of theperipheral area 23, i.e., a thickness of a part of the deposition mask20 where the first recess 30 and the second recess 35 are not formed.Therefore, the thickness t can be said as a thickness of the metal plate21.

In FIG. 4, a minimum angle defined by a line L1, which passes theconnection portion 41 having the minimum cross-sectional area of thethrough-hole 25 and another given position of the wall surface 31 of thefirst recess 30, with respect to the normal direction N of thedeposition mask 20 is represented by a symbol θ1. In order that thediagonally moving deposition material 98 can be caused to reach thesubstrate 92 without being caused to reach the wall surface 31 as muchas possible, it is advantageous that the angle θ1 is increased. In orderto increase the angle θ1, it is effective to reduce the aforementionedwidth β of the top portion 43, as well as to reduce the thickness t ofthe deposition mask 20.

In FIG. 6, the symbol a represents a width of a portion (hereinafteralso referred to as “rib portion”) of the effective area 22 of thesecond surface 21 b of the metal plate 21, which it not etched and thusremains. A width α of the rib portion and a size r₂ of thethrough-portion 42 are suitably determined depending on a size of anorganic EL display device and its display pixels. Table 1 shows examplesof display pixels, a width α of the rib portion and a size r₂ of thethrough-portion which are required depending on the display pixels, inan organic EL display device of 5 inches.

TABLE 1 Width of Size of Through- Display Pixels Rib Portion portion FHD(Full High Definition) 20 μm 40 μm WQHD (Wide Quad High Definition) 15μm 30 μm UHD (Ultra High Definition) 10 μm 20 μm

Although not limited, the deposition mask 20 according to thisembodiment is particularly effective when an organic EL display devicehaving a pixel density of 450 ppi or more is produced. Herebelow, a sizeexample of the deposition mask 20 required for producing an organic ELdisplay device having such a high pixel density is described. FIG. 7 isan enlarged sectional view showing the through-hole 25 of the depositionmask 20 shown in FIG. 4 and an area near thereto.

In FIG. 7, as parameters related to the shape of the through-hole 25, adistance from the second surface 20 b of the deposition mask 20 up tothe connection portion 41 thereof along the normal direction of thedeposition mask 20, i.e., a height of the wall surface 36 of the secondrecess 35 is represented by a symbol r₁. Further, a size of the secondrecess 35 in a part where the second recess 35 is connected to the firstrecess 30, i.e., a size of the through-portion 42 is represented by asymbol r₂. In addition, in FIG. 7, an angle that is defined by a lineL2, which connects the connection portion 41 and a distal edge of thesecond recess 35 in the second surface 21 b of the metal plate 21, withrespect to the normal line N of the metal plate 21 is represented by asymbol θ2.

When an organic EL display device having a pixel density of 450 ppi ormore is produced, the size r₂ of the through-portion 42 is preferablyset within a range of from 10 to 60 μm. Due to this size, it is possibleto provide the deposition mask capable of producing an organic ELdisplay device having a high pixel density. Preferably, the height r₁ ofthe wall surface 36 of the second recess 35 is set 6 μm or less.

Next, the aforementioned angle θ2 shown in FIG. 7 is described. Theangle θ2 corresponds to a maximum value of an inclined angle of thedeposition material 98 that can reach the substrate 92, out of thedeposition material 98 that comes in an inclined manner with respect tothe normal direction N of the metal plate 21 and passes through thethrough-portion 42 near the connection portion 41. This is because thedeposition material 98 coming at an inclined angle greater than theangle θ2 adheres to the wall surface 36 of the second recess 35, beforethe deposition material 98 reaches the substrate 92. Thus, by decreasingthe angle θ2, it can be prevented that the deposition material 98 comingat a large inclined angle and passing through the through-portion 42adheres to the substrate 92. Therefore, it can be prevented that thedeposition material 98 adheres to a portion of the substrate 92, whichis outside a part overlapping with the through-portion 42. Namely, todecrease the angle θ2 can prevent variation in planar dimension andthickness of the deposition material 98 adhering to the substrate 92.From this point of view, the through-hole 25 is formed such that theangle θ2 is 45 degrees or less. FIG. 7 shows the example in which thesize of the second recess 35 in the second surface 21 b, i.e., anopening size of the through-hole 25 in the second surface 21 b is largerthan the size r₂ of the second recess 35 in the connection portion 41.Namely, the value of the angle θ2 is a positive value. However, althoughnot shown, the size r₂ of the second recess 35 at the connection portion41 may be larger than the size of the second recess 35 in the connectionportion 41. Namely, the value of the angle θ2 may be a negative value.

Next, problems that may occur when the deposition mask 20 is producedare described. Firstly, a manufacturing method for the deposition mask20 is schematically described with reference to FIGS. 8(a) to 8(c).

In the manufacturing steps of the deposition mask 20, as shown in FIG.8(a), a metal plate 21 having a first surface 21 a and a second surface21 b is firstly prepared. In addition, as shown in FIG. 8(a), a firstresist pattern 65 a is formed on the first surface 21 a of the metalplate 21, and a second resist pattern 65 b is formed on the secondsurface 21 b. Thereafter, as shown in FIG. 8(b), a second surfaceetching step of forming a second recess 35 is performed by etching anarea of the second surface 21 b of the metal plate 21, which is notcovered with the second resist pattern 65 b. Then, as shown in FIG.8(c), a first etching step of forming a first surface recess 30 isperformed by etching an area of the first surface 21 a of the metalplate 21, which is not covered with the first resist pattern 65 a.

As described above, in order to increase the utilization efficiency ofthe deposition material 98 while the deposition mask 20 has a sufficientstrength, it is preferable that the top portion 43 having a width assmall as possible remains. In this case, in accordance with such a topportion 43, a width w of the first resist pattern 65 a formed on thefirst surface 21 a of the metal plate 21 becomes also smaller. As shownin FIGS. 8(a) and 8(b), erosion in the metal plate 21 by the etchingsteps takes place not only in the normal direction (thickness direction)of the metal plate 21 but also in a direction along the plane of themetal plate 21. Thus, when the width w of the first resist pattern 65 ais smaller than the degree of erosion that takes place in the directionalong the plate plane of the metal plate 21, the resist pattern 65 apeels off from the first surface 21 a of the metal plate 21 during theetching step. The erosion that takes place in the direction along theplate plane of the metal plate 21 is considered to be at least about 3μm on one side. Taking this point into consideration, the width w of thefirst resist pattern 65 a is preferably set to be larger than the widthβ of the aforementioned top portion 43 by at least 6 μm. For example,the width w of the first resist pattern 65 a is within a range of from20 to 40 μm, for example.

In order to precisely create the first resist pattern 65 a of a narrowwidth, a below-described resist film 65 c for forming the resist pattern65 a is required to have a high resolution. For example, a so-called dryfilm such as a resist film containing acryl-based photo-setting resin ispreferably used as the resist film 65 c. An example of the dry film maybe RY3310 manufactured by Hitachi Chemical Co., Ltd. In addition, otherexamples of the dry film may be UFG-052 and ATP-053 manufactured byASAHI KASEI E-materials Corp. and so on.

The dry film means a film that is attached to an object such as themetal plate 21, in order to form a resist film on the object. The dryfilm includes at least a base film made of, e.g., PET, and aphotosensitive layer having photosensitivity, which is laminated on thebase film. The photosensitive layer contains a photosensitive materialsuch as acryl-based resin, an epoxy-based resin, a polyimide-basedresin, a styrene-based resin and so on.

By producing the first resist pattern 65 a by means of a dry film havinga high resolution, it is possible to precisely form the first resistpattern 65 a having a small width w on the first surface 21 a of themetal plate 21. On the other hand, when the width w of the first resistpattern 65 becomes small, a contact planar dimension between the firstsurface 21 a of the metal plate 21 and the first resist pattern 65 abecomes also small. Thus, the below-described resist film 65 c forforming the first resist pattern 65 a is required to have a highadhesion force to the first surface 21 a of the metal plate 21.

However, the present inventors have conducted extensive studies andfound that, although the dry film strongly adheres to copper and copperalloy, the dry film is difficult to adhere to an iron-nickel alloy suchas an invar material. Thus, the conventional manufacturing process ofthe deposition mask 20 has a trouble in which the first resist pattern65 a and/or the second resist pattern 65 b peel/peels off from the metalplate 21. For example, in a developing step of developing thebelow-described exposed resist film 65 c, 65 d to form a resist pattern65 a, 65 b, it was observed that a developing solution penetratedbetween the metal plate 21 and the resist film 65 c, 65 d so that theresist film 65 c, 65 d peeled off from the metal plate 21. In addition,after the developing step and before a baking step of baking the resistpattern 65 a, 65 b in order to more securely adhere the resist pattern65 a, 65 b to the metal plate 21, it was observed that the resist film65 c, 65 d peeled off from the metal plate 21.

As an etching resist, a liquid resist material that is applied to anobject while it is in a flowable state, e.g., in a liquid state iswidely known, in addition to the aforementioned dry film. The liquidresist material is a casein resist, for example. In this case, a resistfilm is formed on an object such as the metal plate 21 by applying theliquid resist material onto the object and solidifying the liquid. Theliquid resist material comes into contact with the object, while it isin the liquid state. Thus, even when the surface of the object has aconcavity and/or convexity, the liquid solidifies to become a resistfilm after the liquid followed the concavity and/or convexity. Thus, anadhesion property between the liquid resist material and the object ishigh.

On the other hand, as described above, the dry film comes into contactwith the object, while it is in the state of a film containing aphotosensitive layer. Thus, when there is concavity and/or convexity onthe surface of the object, the photosensitive layer of the dry filmcannot completely follow the concavity and/or convexity. As a result, anadhesion property between the dry film and the object is lower than theadhesion property between the liquid resist material and the object.

Table 2 shows a comparison result between the dry film and the liquidresist material as to a resolution, an adhesion property and a cost. Theterm “adhesion property” herein means easiness of the dry film or theliquid resist material to the invar material. As shown in Table 2, theconventional dry film is poor in adhesion property to the invar materialand costly, while it has an excellent resolution as compared with theliquid resist material.

TABLE 2 Adhesion Resolution Property Cost Dry Film Great Not good Notgood Liquid Resist Material Not good Good Great

The dry film has been conventionally used for producing a copper wiringby etching a copper foil for a print substrate. In this case, the dryfilm is provided on the copper foil. As described above, since the dryfilm strongly adheres to copper and copper alloy, a problem related tothe adhesion property of the dry film has not specifically drawnattention. It is considered that the problem of poor adhesion propertyof the dry film to an iron-nickel alloy such as invar material drawsattention when a resist pattern of a small width is precisely formed ona metal plate made of an iron-nickel alloy.

In order to stably form the first resist pattern 65 a having a smallwidth w on the first surface 21 a of the metal plate 21 made of aniron-nickel alloy, it is important to improve the adhesion force betweenthe first resist pattern 65 a and the first surface 21 a. The presentinventors have conducted extensive studies and found that the adhesionforce between the first resist pattern 65 a and the first surface 21 adepends on the presence of a nickel compound in the first surface 21 aof the metal plate 21. The fact found by the present inventors isdescribed below.

In general, when a surface of a metal plate made of an iron alloycontaining nickel is oxidized, the metal plate includes a bulk layermade of an iron alloy containing nickel, and a surface layer containingiron oxide, iron hydroxide, nickel oxide and nickel hydroxide. To bespecific, there are iron oxide and iron hydroxide on a part closest tothe surface of the metal plate, and there are nickel oxide and nickelhydroxide between the iron oxide and the iron hydroxide, and the bulklayer.

The present inventors analyzed a composition of the metal plate with itssurface being oxidized by using an X-ray photoelectron spectroscopy(also referred to as XPS method herebelow), and observed that a bulklayer made of an iron alloy containing nickel existed at a positionwithin several nanometers from the surface of the metal plate. Namely,it can be said that a surface layer containing nickel oxide and nickelhydroxide exists at a position within several nanometers from thesurface of the metal plate.

In addition, as shown in the below-described Examples, the presentinventors evaluated an adhesion property of the metal plate to a resistpattern was evaluated, and found that, as compared with a metal platehaving a high adhesion property to a resist pattern, a metal platehaving a low adhesion property to a resist pattern had more nickel oxideand nickel hydroxide in the surface layer of the metal plate. Inconsideration that compounds existing in the surface layer of the metalplate are iron oxide, iron hydroxide, nickel oxide and nickel hydroxide,the condition in which “more nickel oxide and nickel hydroxide exist inthe surface layer of the metal plate” can be said as a condition inwhich “a ratio of nickel oxide and nicely hydroxide relative to ironoxide and iron hydroxide is higher in the surface layer of the metalplate”. In addition, as shown in the below-described Examples, thepresent inventors evaluated adhesion properties of various metal platesto a resist pattern, and found that, when a ratio of nickel oxide andnickel hydroxide relative to iron oxide and iron hydroxide was 0.4 orless, the adhesion property of a metal plate to a resist pattern couldbe sufficiently ensured, and that when the aforementioned ratio exceeded0.4, the adhesion property of a metal plate to a resist pattern wasinsufficient.

In addition, as to a metal plate having a high adhesion property to aresist pattern and a metal plate having a low adhesion property to aresist pattern, the present inventors examined difference inmanufacturing steps between these metal plates. The present inventorsfound that the metal plate having a low adhesion property to a resistpattern was subjected to an annealing step of annealing the metal plateunder a reduction atmosphere containing a lot of reducing gas such ashydrogen. Thus, it can be said that, under a reduction atmosphere,nickel oxide and nickel hydroxide tend to segregate on the surface ofthe metal plate. In addition, as shown in the below-described reactionformula, under a reduction atmosphere containing a lot of reducing gassuch as hydrogen, nickel hydroxide is generated in accordance with areduction reaction of nickel oxide. Thus, it is considered that nickelhydroxide has a larger negative impact on the adhesion property to aresist pattern than nickel oxide does.

Based on the above examination, it can be said that an adhesion propertyof a metal plate to a resist pattern can be expected based on a ratio ofnickel hydroxide in the surface layer of the metal plate. However, asshown in the below-described Examples, in the XPS analysis, it is noteasy to accurately separate a peak corresponding to nickel oxide and apeak corresponding to nickel hydroxide. In consideration thereof, thisembodiment employs a method for obtaining information about the adhesionproperty to a resist pattern, based on a ratio of nickel oxide andnickel hydroxide relative to iron oxide and iron hydroxide. A concreteexistence ratio and details of a method for inspecting respectivecompounds in the first surface 21 a of the metal plate 21 will bedescribed later.

Next, an operation and an effect of this embodiment as structured aboveare described.

Herein, a manufacturing method for a metal plate used for manufacturinga deposition mask is firstly described. Then, a method for manufacturinga deposition mask using the obtained metal plate is described.

After that, a method for depositing a deposition material on a substrateusing the obtained deposition mask is described.

Manufacturing Method for Metal Plate

A method for manufacturing a metal plate is firstly described withreference to FIGS. 9(a) and 9(b). FIG. 9(a) is a view showing a step ofrolling a base metal to obtain a metal plate having a desired thickness.FIG. 9(b) is a view showing a step of annealing the metal plate obtainedby the rolling step.

Rolling Step

As shown in FIG. 9(a), a base metal 55 made of an iron alloy containingnickel is prepared, and the base metal 55 is transported toward arolling apparatus 56 including a pair of reduction rolls 56 a and 56 balong a transport direction shown by the arrow D1. The base metal 55having reached between the pair of reduction rolls 56 a and 56 b isrolled by the pair of reduction rolls 56 a and 56 b. Thus, a thicknessof the base metal 55 is reduced and is elongated along the transportdirection. As a result, a plate member 64X having a thickness t₀ can beobtained. As shown in FIG. 9(a), a winding body 62 may be formed bywinding up the plate member 64X around a core 61. A concrete value ofthe thickness t₀ is within a range of from 5 to 85 μm, as describedabove.

FIG. 9(a) merely shows the rolling step schematically, and a concretestructure and procedure for performing the rolling step are notspecifically limited. For example, the rolling step may include a hotrolling step of processing the base metal at a temperature not less thana recrystallization temperature of the invar material constituting thebase metal 55, and a cold rolling step of processing the base metal at atemperature not more than the recrystallization temperature of the invarmaterial. In addition, an orientation along which the base metal 55 andthe plate member 64X pass through between the reduction rolls 56 a and56 b is not limited to one direction. For example, in FIGS. 9(a) and9(b), the base metal 55 and the plate member 64X may be gradually rolledby repeatedly passing the base metal 55 and the plate member 64X throughbetween the pair of reduction rolls 56 a and 56 b in an orientation fromthe left side to the right side in a sheet plane, and in an orientationfrom the right side to the left side in the sheet plane.

Slitting Step

After that, there may be performed a slitting step of slitting both endsof the plate member 64X, which is obtained by the rolling step, in thewidth direction thereof, over a range of from 3 to 5 mm. The slittingstep is performed to remove a crack that may be generated on both endsof the plate member 64X because of the rolling step. Due to the slittingstep, it can be prevented that a breakage phenomenon of the plate member64X, which is so-called plate incision, occurs from the crack as astarting point.

Annealing Step

After that, in order to remove a remaining stress accumulated by therolling process in the plate member 64X, as shown in FIG. 9(b), theplate member 64X is annealed by using an annealing apparatus 57, so thatan elongated metal plate 64 is obtained. As shown in FIG. 9(b), theannealing step may be performed while the plate member 64X or theelongated metal plate 64 is being pulled in the transport direction(longitudinal direction). Namely, the annealing step may be performed asa continuous annealing process while the elongated metal plate is beingtransported, instead of a batch-type annealing process. A duration ofthe annealing step is suitably set depending on a thickness of theelongated metal plate 64 and a reduction ratio thereof. For example, theannealing step is performed for 60 seconds or more at 500° C. The above“60 seconds” mean that it takes 60 seconds for the plate member 64X topass through a space, which is heated at a temperature of 500° C. in theannealing apparatus 57.

The aforementioned annealing step is preferably performed in anirreducible atmosphere or an inert gas atmosphere. The irreducibleatmosphere herein means an atmosphere free of reducing gas such ashydrogen. The expression “free of reducing gas” means that aconcentration of reducing gas such as hydrogen is 10% or less. Inaddition, the inert gas atmosphere means an atmosphere where inert gassuch as argon gas, helium gas, or nitrogen gas exists 90% or more. Byperforming the annealing step in the irreducible atmosphere or the inertgas atmosphere, it can be prevented that the aforementioned nickelhydroxide is generated on a first surface 64 a and a second surface 64 bof the elongated metal plate 64.

By performing the annealing step, it is possible to obtain the elongatedmetal plate 64 of a thickness t₀, from which the remaining strain isremoved to a certain extent. The thickness t₀ is generally equal to athickness t of the deposition mask 20.

The elongated metal plate 64 having the thickness t₀ may be made byrepeating the above rolling step, the slitting step and the annealingstep a plurality of times. FIG. 9(b) shows the example in which theannealing step is performed while the elongated metal plate 64 is beingpulled in the longitudinal direction. However, not limited thereto, theannealing step may be performed to the elongated metal plate 64 that iswound around the core 61. Namely, the batch-type annealing process maybe performed. When the annealing step is performed while the elongatedmetal plate 64 is wound around the core 61, the elongated metal plate 64may have a warping tendency corresponding to a winding diameter of thewinding body 62. Thus, depending on a winding diameter of the windingbody 62 and/or a material forming the base metal 55, it is advantageousto perform the annealing step while the elongated metal plate 64 isbeing pulled in the longitudinal direction.

Severing Step

After that, there is performed a severing step of severing both ends ofthe elongated metal plate 64 in the width direction thereof over apredetermined range, so as to adjust the width of the elongated metalplate 64 into a desired width. In this manner, the elongated metal plate64 having a desired thickness and a desired width can be obtained.

Inspection Step

After that, there is performed an inspection step of inspecting acomposition of the material constituting the first surface 64 a of theobtained elongated metal plate 64. Herein, there is explained an examplein which a composition analysis of the first surface 64 a of theelongated metal plate 64 is performed by the XPS method. The XPS methodis method in which a specimen is irradiated with an X-ray, and an energydistribution of photoelectrons discharged from the specimen is measuredto obtain information about types of constituent elements and/or anexistence amount thereof in an area within a range of several nanometersfrom a surface of the specimen. In this case, in a spectrum measured bythe X-ray photoelectron spectroscopy, an existence amount of eachconstituent element is proportionate to a peak planar dimension valuecalculated by integrating a peak planar dimension corresponding to eachconstituent element. Thus, a peak planar dimension value correspondingto each constituent element is firstly calculated, a total value of thepeak planar dimension values of the respective constituent elements isthen calculated, and thereafter an atomic % of a target constituentelement can be calculated by dividing a peak planar dimension value ofthe target constituent element by the total value and multiplying thevalue by 100. A relationship between an existence amount of a givenconstituent element and a peak planar dimension value thereof may differfrom one another depending on sensitivity to an X-ray and so on. In thiscase, the aforementioned total value and the atomic % may be calculatedafter a peak planar dimension value of each constituent element ismultiplied by a relative sensitivity coefficient for compensating thesensitivity difference so as to calculate a compensated peak planardimension value.

FIG. 10 is a view showing that a composition analysis of the firstsurface 64 a of the elongated metal plate 64 is performed by using theX-ray photoelectron spectroscopy. As shown in FIG. 10, in one example ofthe composition analysis of the first surface 64 a of the elongatedmetal plate 64, an X-ray X1 is emitted from an irradiation unit 81 tothe elongated metal plate 64, and an acceptance angle of a photoelectronX2 discharged from the elongated metal plate 64 is set at 90 degrees. Inthis case, types of constituent elements and their existence amounts inan area within a range of several nanometers, e.g., 5 nm from the firstsurface 64 a of the elongated metal plate 64 can be measured in animproved reproducible fashion. As shown in FIG. 10, the “acceptanceangle” is an angle defined by a direction along which the photoelectronX2, which is to be discharged from the elongated metal plate 64 to reacha detection unit 82, travels when the photoelectron X2 is dischargedfrom the elongated metal plate 64, and the first surface 64 a of theelongated metal plate 64.

After the composition analysis of the first surface 64 a of theelongated metal plate 64 was performed by means of the XPS method, thereis performed selection of an elongated metal plate 64 in which only theelongated metal plate 64 that satisfies the following condition (1) isused in a manufacturing step of the deposition mask 20, which isdescribed below.

(1) When the composition analysis of the first surface 64 a of theelongated metal plate 64 is performed by using the X-ray photoelectronspectroscopy, a ratio A1/A2 obtained by the result of the X-rayphotoelectron spectroscopy is 0.4 or less, where A1 is a sum of a peakplanar dimension value of nickel oxide and a peak planar dimension valueof nickel hydroxide, and A2 is a sum of a peak planar dimension value ofiron oxide and a peak planar dimension value of iron hydroxide.

The aforementioned condition (1) is a condition for sufficientlyensuring an adhesion force between the below-described first resistpattern 65 a and the first surface 21 a. As described above, nickelhydroxide and nickel oxide function so as to decrease the adhesion forcebetween the first resist pattern 65 a and the first surface 21 a. Thus,determining upper limits of nickel oxide and a peak planar dimensionvalue of nickel oxide, as determined by the aforementioned condition(1), is effective to ensure a minimum adhesion force required as theadhesion force between the first resist pattern 65 a and the firstsurface 21 a.

As described later, in an analysis using the X-ray photoelectronspectroscopy, since a peak corresponding to nickel oxide and a peakcorresponding to nickel hydroxide exist extremely close to each other,it is difficult to definitely differentiate these peaks. Similarly,since a peak corresponding to iron oxide and a peak corresponding toiron hydroxide exist extremely close to each other, it is difficult todefinitely differentiate these peaks. From this analytic point of view,in this embodiment, whether an adhesion force between the first resistpattern 65 a and the first surface 21 a can be sufficiently ensured ornot is judged based on a ratio between a sum of a peak planar dimensionvalue of nickel oxide and a peak planar dimension value of nickelhydroxide, and a sum of a peak planar dimension value of iron oxide anda peak planar dimension value of iron hydroxide, instead of a ratiobetween a peak planar dimension value of nickel hydroxide and a peakplanar dimension value of iron hydroxide.

The present inventors have conducted extensive studies and found that,when an atmosphere upon annealing step contains reducing gas such ashydrogen, nickel hydroxide is likely to be generated on the firstsurface 64 a and the second surface 64 b of the elongated metal plate64, so that the adhesion force between the first resist pattern 65 a andthe first surface 21 a is likely to decrease. When an atmosphere uponannealing step was an irreducible atmosphere or an inert gas atmosphere,it could be prevented that nickel hydroxide was generated on the firstsurface 64 a and the second surface 64 b of the elongated metal plate64. Thus, since the above A1/A2 was made to be 0.4 or less, an adhesionforce between the first resist pattern 65 a and the first surface 21 acould be sufficiently ensured.

Under a reduction atmosphere containing reducing gas such as hydrogen,as shown by the below reaction formula, it is considered that a part ofnickel oxide, which has been already formed on the surface of theelongated metal plate 64, is reduced to generate nickel, and that,simultaneously therewith, nickel hydroxide is generated on the surfaceof the elongated metal plate 64.2NiO+H₂→Ni(OH)₂Ni

In order to sufficiently ensure the adhesion force between the firstresist pattern 65 a and the first surface 21 a, it is important thatgeneration of a nickel reduction reaction on the surface of theelongated metal plate 64, such as the first surface 64 a and the secondsurface 64 b, so as to prevent generation of nickel hydroxide.

The present inventors have conducted extensive studies and found that,as A1/A2 becomes lower, the adhesion property between the first resistpattern 65 a and the first surface 21 a tends to increase. Thus, inorder to improve the adhesion property between the first resist pattern65 a and the first surface 21 a, A1/A2 is preferably 0.3 or less, andmore preferably A1/A2 is 0.2 or less.

In the above description, the inspection step of inspecting theelongated metal plate 64 based on the aforementioned condition (1) isutilized for selecting the elongated metal plate 64, for example.However, the use of the condition (1) is not limited thereto.

For example, the aforementioned condition (1) may be utilized foroptimizing a condition of manufacturing the elongated metal plate 64,such as an annealing temperature, an annealing period of time and so on.To be specific, the condition (1) may be utilized for an operation inwhich the elongated metal plates 64 are manufactured at variousannealing temperatures for various annealing periods of time,compositions of a surface of each obtained elongated metal plate 64 areanalyzed, and the analysis result and the condition (1) are compared toeach other so as to set a suitable manufacturing condition thatsatisfies the condition (1). In this case, it is not necessary that theselection based on the condition (1) is performed for all the elongatedmetal plates 64 obtained in the actual manufacturing steps. For example,a sampling inspection regarding the condition (1) may be performed onlyfor some of the elongated metal plates 64. Alternatively, after amanufacturing condition has been once set, the inspection regarding thecondition (1) may not be performed at all.

Method for Manufacturing Deposition Mask

Next, a method for manufacturing the deposition mask 20 by using theelongated metal plate 64 selected as described above is described withreference mainly to FIGS. 11 to 19. In the below-described method formanufacturing the deposition mask 20, as shown in FIG. 11, the elongatedmetal plate 64 is supplied, the through-holes 25 are formed in theelongated metal plate 64, and the elongated metal plate 64 are severedso that the deposition masks 20 each of which is formed of thesheet-like metal plate 21 are obtained.

To be more specific, the method for manufacturing a deposition mask 20includes a step of supplying an elongated metal plate 64 that extendslike a strip, a step of etching the elongated metal strip 64 using thephotolithographic technique to form a first recess 30 in the elongatedmetal plate 64 from the side of a first surface 64 a, and a step ofetching the elongated metal plate 64 using the photolithographictechnique to form a second recess 35 in the elongated metal plate 64from the side of a second surface 64 b. When the first recess 30 and thesecond recess 35, which are formed in the elongated metal plate 64,communicate with each other, the through-hole 25 is made in theelongated metal plate 64. In the example shown in FIGS. 12 to 19, thestep of forming the second recess 35 is performed before the step offorming the first recess 30. In addition, between the step of formingthe second recess 35 and the step of forming the first recess 30, thereis further provided a step of sealing the thus made second recess 35.Details of the respective steps are described below.

FIG. 11 shows a manufacturing apparatus 60 for making the depositionmasks 20. As shown in FIG. 11, the winding body 62 having the core 61around which the elongated metal plate 64 is wound is firstly prepared.By rotating the core 61 to unwind the winding body 62, the elongatedmetal plate 64 extending like a strip is supplied as shown in FIG. 11.After the through-holes 25 are formed in the elongated metal plate 64,the elongated metal plate 64 provides the sheet-like metal plates 21 andfurther the deposition masks 20.

The supplied elongated metal plate 64 is transported by the transportrollers 72 to an etching apparatus (etching means) 70. The respectiveprocesses shown in FIGS. 12 to 19 are performed by the etching means 70.In this embodiment, a plurality of the deposition masks 20 are assignedin the width direction of the elongated metal plate 64. Namely, thedeposition masks 20 are made from an area occupying a predeterminedposition of the elongated metal plate 64 in the longitudinal direction.In this case, it is preferable that the deposition masks 20 are assignedto the elongated metal plate 64 such that the longitudinal direction ofeach deposition mask 20 corresponds to the rolling direction D1 of theelongated metal plate 64.

As shown in FIG. 12, resist films 65 c and 65 d each containing anegative-type photosensitive resist material are firstly formed on thefirst surface 64 a and the second surface 64 b of the elongated metalplate 64. As a method for forming the resist films 65 c and 65 d, thereis employed a method in which a film on which a layer containing aphotosensitive resist material, such as an acryl-based photo-settingresin is formed, i.e., a so-called dray film is attached to the firstsurface 64 a and the second surface 64 b of the elongated metal plate64. As described above, the elongated metal plate 64 is manufacturedsuch that an existence amount of nickel hydroxide in the first surface64 a satisfies the aforementioned condition (1). The resist film 65 c isattached to such a first surface 64 a.

Then, exposure masks 85 a and 85 b which do not allow light to transmitthrough areas to be removed of the resist films 65 c and 65 d areprepared. As shown in FIG. 13, the masks 85 a and 85 b are located onthe resist films 65 c and 65 d. For example, glass dry plates which donot allow light to transmit through the areas to be removed from theresist films 65 c and 65 d are used as the exposure masks 85 a and 85 b.Thereafter, the exposure masks 85 a and 85 b are sufficiently broughtinto tight contact with the resist films 65 c and 65 d by vacuumbonding.

A positive-type photosensitive resist material may be used. In thiscase, there is used an exposure mask which allows light to transmitthrough an area to be removed of the resist film.

After that, the resist films 65 c and 65 d are exposed through theexposure masks 85 a and 85 b. Further, the resist films 65 c and 65 dare developed (developing step) in order to form an image on the exposedresist films 65 c and 65 d. Thus, as shown in FIG. 14A, a first resistpattern 65 a can be formed on the first surface 64 a of the elongatedmetal plate 64, and a second resist pattern 65 b can be formed on thesecond surface 64 b of the elongated metal plate 64. The developing stepmay include a resist heating step for increasing a hardness of theresist films 65 c and 65 d, or for more securely adhering the resistfilms 65 c and 65 d to the elongated metal film 64. The resist heatingstep is performed in an atmosphere of inert gas such as argon gas,helium gas, nitrogen gas or the like, at a temperature within a range offrom 100 to 400° C., for example.

FIG. 14B is a partial plan view of the elongated metal plate 64 of FIG.14A on which the first and second resist patterns 65 a and 65 b areprovided, when seen from the side of the first surface 64 a. In FIG.14B, an area on which the first resist pattern 64 a is provided isshaded. In addition, a first recess 30, a wall surface 31, a connectionportion 41 and a top portion 43, which are to be formed by thesucceeding etching step, are shown by dotted lines.

Then, as shown in FIG. 15, there is performed a second surface etchingstep of etching the area of the second surface 64 b of the elongatedmetal plate 64, which is not covered with the second resist pattern 65b, by using a second etchant. For example, the second etchant is ejectedfrom a nozzle, which is disposed on the side facing the second surface64 b of the transported elongated metal plate 64, toward the secondsurface 64 b of the elongated metal plate 64 through the second resistpattern 65 b. As a result, as shown in FIG. 15, areas of the elongatedmetal plate 64, which are not covered with the resist pattern 65 b, areeroded by the second etchant. Thus, a lot of second recesses 35 areformed in the second surface 64 b of the elongated metal plate 64. Thesecond etchant to be used is an etchant containing ferric chloridesolution and hydrochloric acid.

After that, as shown in FIG. 16, the second recesses 35 are coated witha resin 69 resistant to a first etchant that is used in a succeedingfirst surface etching step. Namely, the second recesses 35 are sealed bythe resin 69 resistant to the first etchant. In the example shown inFIG. 16, a film of the resin 69 is formed to cover not only the formedsecond recesses 35 but also the second surface 64 b (resist pattern 65b).

Then, as shown in FIG. 17, there is performed the first surface etchingstep of etching an area of the first surface 64 a of the elongated metalplate 64, which is not covered with the first resist pattern 65 a, toform a first recess 30 in the first surface 64 a. The first surfaceetching step is performed until each second recess 35 and each firstrecess 30 communicate with each other so that a through-hole 25 isformed. Similarly to the aforementioned second etchant, the firstetchant to be used is an etchant containing ferric chloride solution andhydrochloric acid.

The erosion by the first etchant takes place in a portion of theelongated metal plate 64, which is in contact with the first etchant.Thus, the erosion develops not only in the normal direction (thicknessdirection) of the elongated metal plate 64 but also in a direction alongthe plate plane of the elongated metal plate 64. Preferably, the firstsurface etching step is finished before the two first recesses 30, whichare respectively formed at positions facing two adjacent holes 66 a ofthe resist pattern 65 a, are merged with each other on a reverse side ofa bridge portion 67 a positioned between the two holes 66 a. Thus, asshown in FIG. 18, the aforementioned top portion 43 can be left on thefirst surface 64 a of the elongated metal plate 64.

After that, as shown in FIG. 19, the resin 69 is removed from theelongated metal plate 64. For example, the resin 69 can be removed byusing an alkali-based peeling liquid. When the alkali-based peelingliquid is used, as shown in FIG. 19, the resist patterns 65 a and 65 bare removed simultaneously with the removal of the resin 69. However,after the removal of the resin 69, the resist patterns 65 a and 65 b maybe removed separately from the resin 69.

The elongated metal plate 64 having a lot of through-holes 25 formedtherein in the above manner is transported to a severing apparatus(severing means) 73 by the transport rollers 72, 72 which are rotatedwhile sandwiching therebetween the elongated metal plate 64. Theabove-described supply core 61 is rotated through a tension (tensilestress) that is applied by the rotation of the transport rollers 72, 72to the elongated metal plate 64, so that the elongated metal plate 64 issupplied from the winding body 62.

Thereafter, the elongated metal plate 64 in which a lot of through-holes25 are formed is severed by the severing apparatus (severing means) 73to have a predetermined length and a predetermined width, whereby thesheet-like metal plates 21 having a lot of through-holes 25 formedtherein can be obtained.

In this manner, the deposition mask 20 formed of the metal plate 21 witha lot of through-holes 25 formed therein can be obtained. According tothis embodiment, the elongated metal plate 64 from which the metal plate21 is originated is manufactured such that an existence amount of nickelhydroxide in the first surface 64 a satisfies the above condition (1).The aforementioned resist pattern 65 a and the resist film 65 c fromwhich the resist pattern 65 a is originated are attached to such a firstsurface 64 a. Thus, the adhesion force between the first surface 64 a ofthe elongated metal plate 64 and the first resist pattern 65 c can besufficiently ensured. In addition, as the resist film 65 c, a so-calleddry film having a high resolution, such as a resist film containing anacryl-based photo-setting resin, is used. Thus, according to thisembodiment, the first resist pattern 65 a of a narrow width can beprecisely formed on the first surface 64 a of the elongated metal plate64, while preventing a trouble such as peeling of the first resistpattern 65 a from the metal plate 21. Thus, the deposition mask 20 usedfor producing an organic EL display device having a high pixel densitycan be manufactured with a high throughput.

In addition, according to this embodiment, since the first resistpattern 65 a with a desired width can be precisely formed on the firstsurface 64 a of the elongated metal plate 64, the deposition mask 20having the top portion 43 with a desired width β can be produced. Thus,the aforementioned angle θ1 can be increased as much as possible, whilethe deposition mask 20 has a sufficient strength.

Deposition Step

Next, there is explained a method for depositing the deposition materialonto the substrate 92 by using the obtained deposition mask 20. As shownin FIG. 2, the second surface 20 b of the deposition mask 20 is firstlybrought into tight contact with the substrate 92. At this time, thesecond surface 20 b of the deposition mask 20 may be brought into tightcontact with the surface of the substrate 92, with the use of magnets,not shown. In addition, as shown in FIG. 1, the deposition masks 20 areattached to the frame 15 in a taut state, so that the surface of eachdeposition mask 20 is in parallel with the surface of the glasssubstrate 92. Thereafter, by heating the deposition material 98 in thecrucible 94, the deposition material 98 is evaporated or sublimated. Theevaporated or sublimated deposition material 98 adheres to the substrate92 through the through-holes 25 in the deposition masks 20. As a result,a film of the deposition material 98 is formed on the surface of thesubstrate 92 in a desired pattern corresponding to the positions of thethrough-holes 25 of the deposition masks 20.

According to this embodiment, since the top portion 43 having a desiredwidth β can be left on the side of the first surface 20 a, thedeposition mask 20 can have a sufficient strength.

The aforementioned embodiment can be variously modified. Herebelow,modification examples are described with reference to the drawingsaccording to need. In the below description and the drawings used in thebelow description, a part that can be similarly constituted to the aboveembodiment has the same symbol as that of corresponding part the aboveembodiment, and overlapped description is omitted. In addition, when theeffect obtained by the aforementioned embodiment is apparently obtainedin the modification examples, description thereof is possibly omitted.

In the aforementioned embodiment, the “first surface” specified by theaforementioned condition (1) is a surface of the elongated metal plate64 or the metal plate 21, on which the deposition material 98 isdisposed on the deposition step. However, the “first surface” specifiedby the aforementioned condition (1) may be a surface of the elongatedmetal plate 64 or the metal plate 21, on which the substrate 92 isdisposed. In this case, a resist pattern to be attached to the side ofthe elongated metal plate 64 or the metal plate 21, on which thesubstrate 92 is disposed, can be securely adhered to the elongated metalplate 64 or the metal plate 21. Thus, recesses can be precisely formedon the side of the elongated metal plate 64 or the metal plate 21, onwhich the substrate 92 is disposed, with a high throughput.

Namely, in this embodiment, the aforementioned condition (1) can be saidas below.

“When a composition analysis of at least a surface of one surface of ametal plate and the other surface located oppositely to the one surfaceis performed by using the X-ray photoelectron spectroscopy, a ratioA1/A2 obtained by the result of the X-ray photoelectron spectroscopy is0.4 or less, where A1 is a sum of a peak planar dimension value ofnickel oxide and a peak planar dimension value of nickel hydroxide, andA2 is a sum of a peak planar dimension value of iron oxide and a peakplanar dimension value of iron hydroxide.”

In addition, according to this embodiment, when the result of thecomposition analysis of at least a surface of one surface of the metalplate and the other surface thereof located oppositely to the onesurface satisfies the aforementioned condition, recesses can beprecisely formed in the surface of the meal plate with a highthroughput.

In addition, the condition in which “a ratio A1/A2 obtained by theresult of the X-ray photoelectron spectroscopy is 0.4 or less, where A1is a sum of a peak planar dimension value of nickel oxide and a peakplanar dimension value of nickel hydroxide, and A2 is a sum of a peakplanar dimension value of iron oxide and a peak planar dimension valueof iron hydroxide” may be satisfied by both the first surface 64 a andthe second surface 64 b of the metal plate 64.

In addition, in the aforementioned embodiment, a plurality of thedeposition masks 20 are assigned in the width direction of the elongatedmetal plate 64. In addition, in the deposition step, the plurality ofdeposition masks 20 are mounted on the frame 15. However, not limitedthereto, as shown in FIG. 20, there may be used deposition masks 20having a plurality of the effective areas 22 arranged like a grid alongboth the width direction and the longitudinal direction of the metalplate 21.

In addition, in the aforementioned embodiment, the resist heating stepis performed in the developing step. However, when the elongated metalplate 64 is manufactured to satisfy the aforementioned condition (1)whereby the adhesion force between the elongated metal plate 64 and theresist film 65 c can be sufficiently ensured, the resist heating stepmay be omitted. When the resist heating step is not performed, thehardness of the first resist pattern 65 a is lower than a case in whichthe resist heating step is performed. Thus, after the through-holes 25have been formed, the resist pattern 65 a can be more easily removed.

In addition, in the aforementioned embodiment, a metal plate having adesired thickness is obtained by rolling a base metal to produce a platemember, and then by annealing the plate member. However, not limitedthereto, a metal plate having a desired thickness may be manufactured bya foil creating step utilizing a plating process. In the foil creatingstep, for example, while a drum made of stainless, which is partiallyimmersed in a plating liquid, is rotated, a plating film is formed on asurface of the drum. By peeling off the plating film, an elongated metalplate can be manufactured in a roller-to-roller manner. When a metalplate is manufactured of an iron alloy containing nickel, a mixturesolution of a solution containing a nickel compound and a solution of aniron compound may be used as a plating liquid. For example a mixturesolution of a solution containing nickel sulfamate and a solutioncontaining iron sulfamate may be used, for example. An additive such asmalonic acid or saccharin may be contained in the plating liquid.

Then, the aforementioned annealing step may be performed to the metalplate obtained in this manner. In addition, after the annealing step,there may be performed the aforementioned severing step of severing bothends of the metal plate, so as to adjust the width of the metal plateinto a desired width.

Also when a metal plate is produced by utilizing a plating process, byperforming the step of forming the resist patterns 65 a and 65 b and thestep of etching the first surface and the second surface of the metalplate, the deposition mask with the plurality of through-holes 25 formedtherein can be obtained, similarly to the aforementioned embodiment. Inaddition, the use of the condition (1) can optimize the judgment of ametal plate and manufacturing conditions.

EXAMPLES

Next, the present invention is described in more detail based onexamples, and the present invention is not limited to the belowdescription of the examples unless the present invention departs fromits spirit.

Example 1

First Winding Body

A base metal made of an iron alloy containing 34 to 38 mass % of nickel,chrome, balancing iron and unavoidable impurities was prepared. Then,the base metal was subjected to the rolling step, the slitting step andthe annealing step, which are described above, so that a winding body(first winding body) around which an elongated metal plate having athickness of 20 μm was wound was manufactured.

Composition Analysis

After that, the elongated metal plate 64 was cut out by using a shearinto a predetermined range, e.g., 30×30 mm, so as to obtain a firstspecimen. Then, a composition of a surface of the first specimen wasanalyzed by means of the XPS method. As a measuring apparatus, an XPSapparatus ESCALAB 220i-XL manufactured by Thermo Fisher ScientificCompany was used.

The XPS apparatus was set as follows upon the composition analysis.

Incident X-ray: monochromated A1 ka (monochromated X-ray, hv=1486.6 eV)

X-ray output: 10 kV·16 mA (160W)

Aperture opening degree: F.O.V.=open, A.A.=open

Measured area: 700 μmø

X-ray incident angle ø1 (see FIG. 10): 45 degrees

Photoelectron acceptance angle: 90 degrees

FIGS. 21(a) and 21(b) show results of analysis of the first specimen cutout from the first winding body by means of the XPS apparatus. In FIGS.21(a) and 21(b), the axis of abscissa shows a photoelectron bindingenergy (Binding Energy) of an electron orbit of the first specimen,which corresponds to an intensity photoelectrons observed from the firstspecimen, and the axis of coordinate shows an intensity of thephotoelectrons observed from the first specimen. FIG. 21(a) shows a casein which the value of the axis of abscissa is about 700 to 740 eV, andFIG. 21(b) shows a case in which the value of the axis of abscissa isabout 850 to 890 eV.

In the composition analysis using the XPS method, a peak whichcorresponds to a content of a constituent element contained in the firstspecimen appears at a given position corresponding to the constituentelement in the axis of abscissa. For example, in FIG. 21(a), a peakindicated by the symbol P1 corresponds to iron oxide and iron hydroxidecontained in the first specimen, and a peak indicated by the symbol P2corresponds to iron contained in the first specimen. In addition, inFIG. 21(b), a peak indicated by the symbol P3 corresponds to nickeloxide and nickel hydroxide contained in the first specimen, and a peakindicated by the symbol P4 corresponds to nickel contained in the firstspecimen.

As a reference, FIG. 22(a) shows a result of analyzing nickel oxide(NiO), which was prepared as a first reference specimen, by means of theXPS method. In addition, FIG. 22(b) shows a result of analyzing nickelhydroxide (Ni(OH)₂), which was prepared as a second reference specimen,by means of the XPS method. As shown in FIG. 22(a), a peak correspondingto nickel oxide appears at a position where the axis of abscissa valueis a first value E1=853.8 eV. On the other hand, as shown in FIG. 22(b),a peak corresponding to nickel hydroxide appears at a position where theaxis of abscissa value is a second value E2=855.9 eV.

In FIG. 21(b), as a reference, a position of the first value E1 at whichthe peak corresponding to nickel oxide appears, and a position of thesecond value E2 at which the peak corresponding to the nickel hydroxideappears are shown by the dotted lines. Since the values of E1 and E2 areclose to each other, as shown in FIG. 21(b), in the measurement resultof the first specimen, the peak P3 includes both a detection result ofphotoelectrons corresponding to nickel oxide and a detection result ofphotoelectrons corresponding to nickel hydroxide. It is not easy toaccurately separate the peak P3 shown in FIG. 21(b) into a peakcorresponding to nickel oxide and a peak corresponding to nickelhydroxide. In consideration of this point, in the aforementionedcondition (1), an adhesion force between the metal plate and the resistpattern is evaluated by using a value which is a sum of the detectionresult of photoelectrons corresponding to nickel oxide and the detectionresult of photoelectrons corresponding to nickel hydroxide.

After the peaks P1 to P4 shown in FIGS. 21(a) and 21(b) had beenmeasured, peak planar dimension values were calculated by integratingthe planar dimensions of the respective peaks. The results were: thepeak planar dimension value of the peak P1 corresponding to the ironoxide and iron hydroxide was 22329.3, the peak planar dimension value ofthe peak P2 corresponding to iron was 4481.8, the peak planar dimensionvalue of the peak P3 corresponding to the nickel oxide and nickelhydroxide was 9090.5, and the peak planar dimension value of the peak P4corresponding to nickel was 4748.9. Thus, when a sum of the peak planardimension value of nickel oxide and the peak planar dimension value ofnickel hydroxide is represented as A1, and a sum of the peak planardimension value of iron oxide and the peak planar dimension value ofiron hydroxide is represented as A2, A1/A2=0.41. Thus, it can be saidthat the first winding body from which the first specimen was taken outdoes not satisfy the aforementioned condition (1).

The peak planar dimension values of the respective peaks P1 to P4 werecalculated by means of an analysis function of the XPS apparatus. Inorder to prevent that a measuring result varies depending on ananalyzer, the Shirley method was always employed as a backgroundcalculating method.

A method for calculating the above A1/A2 based on the analysis result bymeans of the XPS method is described in detail herebelow.

1. Adjustment of XPS Apparatus

Firstly, adjustment of a spectrograph energy axis of the XPS wasperformed to satisfy the following adjustment conditions 1 to 3.

Adjustment condition 1: Ag 3d_(5/2) 368.26±0.05 eV

Adjustment condition 2: Au 4f_(7/2) 83.98±0.05 eV

Adjustment condition 3: Cu 2p_(3/2) 932.67±0.05 eV

The adjustment condition 1 means that the spectrograph energy axis wasadjusted such that a photoelectron binding energy obtained based on asilver 3d_(5/2) orbit was within a range of 368.26±0.05 eV. Similarly,the adjustment condition 2 means that the spectrograph energy axis wasadjusted such that a photoelectron binding energy obtained based on agold 4f_(7/2) orbit was within a range of 83.98±0.05 eV. Similarly, theadjustment condition 3 means that the spectrograph energy axis wasadjusted such that a photoelectron binding energy obtained based on acopper 2p_(3/2) orbit was within a range of 932.67±0.05 eV.

In addition, a charge-up correction of the XPS apparatus was set suchthat a photoelectron biding energy obtained based on C—C bond of acarbon 1s orbit was within a range of 284.7 to 285.0 (eV).

After that, a specimen made of an iron-nickel alloy was analyzed bymeans of the XPS apparatus as adjusted above, and the aforementionedA1/A2 was calculated. A method for calculating the aforementioned A2based on the peaks P1 and P2 on iron is firstly described with referenceto FIGS. 27A to 27D.

2. Analysis on Iron

FIG. 27A shows in enlargement a result of analyzing a certain specimenmade of an iron-nickel alloy by means of the XPS apparatus, inparticular, a result in which an axis of abscissa value is within arange of from 700 to 740 eV. As shown in FIG. 27A, the result in whichthe axis of abscissa value is within a range of from 700 to 740 eVincludes a graph showing an intensity distribution of photoelectronsobtained based on an iron 2p_(1/2) orbit, and a graph showing anintensity distribution of photoelectrons obtained based on an iron2p_(3/2) orbit. Herein, there is described an example in which theaforementioned A2 was calculated based on the graph showing an intensitydistribution of photoelectrons obtained based on an iron 2p_(3/2) orbit(referred to as “iron total peak P_Fe” herebelow).

Calculating Step of Background Line

A step of calculating a background line BG_Fe in the iron total peakP_Fe is firstly described. A lower limit value B1 and an upper limitvalue B2 of values of a photoelectron binding energy of the axis ofabscissa in the 2p_(3/2) orbit of iron to be analyzed were determined asfollows.

Lower limit value B1: 703.6±0.2 eV

Upper limit value B2: 717.0±0.2 eV

Then, a background line BG_Fe in the iron total peak P_Fe within therange of from the lower limit value B1 to the upper limit value B2 wascalculated by using the Shirley method. The “±0.2 eV” in the above lowerlimit value B1 and the upper limit value B2 means that values of thelower limit value B2 and the upper limit value B2 were slightly adjustedfor each specimen, in order that noises of a measurement result did notaffects a calculation result of the background line BG_Fe.

Separation Step of Peak on Iron Alone

Next, a step of separating a peak on iron alone from the iron total peakP_Fe is described in FIG. 27B. FIG. 27B is a view showing in enlargementthe iron total peak P_Fe shown in FIG. 27A. Herein, there is explained aresult of separating the peak on iron alone from the iron total peakP_Fe after the iron total peak P_Fe was subjected to a smoothingprocess. As the smoothing method, a known method such as averaging orthe like may be employed.

A peak position E_Fe1 of a peak on iron alone was firstly determined. Tobe specific, it was determined whether a peak that appeared in relationto iron alone was the peak P1 or P2 included in the iron total peakP_Fe. In the field of XPS method, it is known that a photoelectronbinding energy based on a 2p_(3/2) orbit of iron alone is about 707 eV.Thus, the peak P2 was identified as the peak that appeared in relationto iron alone. Then, a position of the peak P2 was searched. When a peakposition of the peak P2 was within a range of 706.9±0.2 eV, the positionof the peak P2 was employed as the peak position E_Fe1 of the peak oniron alone.

Then, a half-value width W_Fe1 of the peak on iron alone was set at 1.54eV. Thereafter, by using the analysis function of the XPS apparatus, apeak whose peak position was E_Fe1 and whose half-value width was W_Fe1was separated from the iron total peak P_Fe. In FIG. 27B, the thusobtained peak on iron alone is indicated by the symbol P_Fe1. In theanalysis by the XPS apparatus, there is a possibility that a half-valuewidth of the obtained peak P_Fe1 varies from the set half-value widthW_Fe1. In this case, variation within a range of ±0.1 eV was allowed.

In the terms related to the iron total peak P_Fe, the aforementioned“peak P_Fe1 on iron alone” and the below described “peak P_Fe2” and“peak P_Fe3” are peaks obtained by resolving the iron total peak P_Feinto a plurality of peaks based on an element alone and a compoundcontained in a specimen Namely, the aforementioned “peaks P1 and P2” arepeaks discriminated by the shape of the iron total peak P_Fe, and “peaksP_Fe1, P_Fe2 and P_Fe3” are peaks obtained by resolving the iron totalpeak P_Fe based on a physical theory.

Calculating Step of Peak Planar Dimension on Iron Alone

Then, a planar dimension S_Fe1 of the peak P_Fe1 of iron alone wascalculated. The planar dimension S_Fe1 is a planar dimension of an area(hatched area) surrounded by the peak P_Fe1 and the background lineBG_Fe in FIG. 27C.

In addition, a planar dimension of the iron total peak P_Fe wascalculated. The planar dimension of the iron total peak P_Fe is a planardimension of an area surrounded by the iron total peak P_Fe and theBackground line BG_Fe in FIG. 27C.

Then, a planar dimension S_Fe (REST) shown in FIG. 27C was calculated bysubtracting the planar dimension S_Fe1 of the peak P_Fe1 on iron alonefrom the planar dimension of the iron total peak P_Fe. The planardimension S_Fe (REST) as calculated above was used as the aforementionedA2, i.e., the sum of the peak planar dimension value of iron oxide andthe peak planar dimension value of iron hydroxide.

For the purpose of reference, FIG. 27D shows a result of separating thetotal peak P_Fe on the assumption that the iron total peak P_Fe includesthe following three peaks, i.e., the peak P_Fe1, the peak P_Fe2 and thepeak P_Fe3. As described above, the peak P_Fe1 is a peak on iron alone.In addition, the peak P_Fe2 and the peak P_Fe3 are a peak on iron oxideand a peak on iron hydroxide.

When the iron total peak P_Fe is separated into a plurality of peaks asshown in FIG. 27D, the aforementioned planar dimension S_Fe (REST)corresponds to a total sum of the peak planar dimensions except the peakP_Fe1 on iron alone. Namely, the planar dimension S_Fe (REST)corresponds to the sum of the peak planar dimension of iron oxide andthe peak planar dimension value of the iron hydroxide.

Although the position at which a peak on iron alone has been alreadyknown, there are a plurality of positions about iron oxide and ironhydroxide. Thus, a peak on iron oxide and a peak on iron hydroxide donot necessarily appear like the two peaks (peak P_Fe2 and peak P_Fe3)shown in FIG. 27. Thus, it is difficult to accurately calculate a rateof iron oxide or iron hydroxide in a surface layer of a specimen. Takingthis point into consideration, the sum of the peak planar dimension ofiron oxide and peak planar dimension value of iron hydroxide is employedas the aforementioned A2.

The planar dimension S_Fe1 of the peak P_Fe1 on iron alone is sometimesreferred to as a planar dimension value of the peak P2, and the planardimension S_Fe (REST) is sometimes referred to as a planar dimensionvalue of the peak P1.

3. Analysis on Nickel

Next, analysis on nickel is described. FIG. 28A shows in enlargement aresult of analyzing a certain specimen made of an iron-nickel alloy bymeans of the XPS apparatus, in particular, a result in which an axis ofabscissa value is in the range of from 850 to 890 eV. As shown in FIG.28A, the result in which an axis of abscissa value is in the range offrom 850 to 890 eV includes a graph showing an intensity distribution ofphotoelectrons obtained based on a nickel 2p_(1/2) orbit, and a graphshowing an intensity distribution of photoelectrons obtained based on anickel 2p_(3/2) orbit. Herein, there is described an example in whichthe aforementioned A1 was calculated based on the graph showing anintensity distribution of photoelectrons obtained based on a nickel2p_(3/2) orbit (referred to as “nickel total peak P_Ni” herebelow).About a process in the method for calculating A1, which is similar tothat of the calculating method for A2 for iron, detailed descriptionthereof is omitted.

Calculating Step of Background Line

A background line BG_Ni in the nickel total peak P_Ni was calculated byusing the Shirley method. A lower limit value B3 and an upper limitvalue B4 of values of a photoelectron binding energy of the axis ofabscissa in the 2p_(3/2) orbit of nickel to be analyzed were determinedas follows.

Lower limit value B3: 849.5±0.2 eV

Upper limit value B4: 866.9±0.2 eV

Separation Step of Peak on Nickel Alone

Then, as shown in FIG. 28B, a peak on nickel alone was separated fromthe nickel total peak P_Ni. To be specific, in the nickel total peakP_Ni, a peak position of the peak P4 that appeared in relation to nickelalone was searched. When a peak position of the peak P4 is within arange of 852.6±0.2 eV, the position of the peak P4 was employed as thepeak position E_Ni1 of the peak on nickel alone.

Then, a half-value width W_Ni1 of the peak on nickel alone was set at1.15 eV. Thereafter, by using the analysis function of the XPSapparatus, a peak whose peak position was E_Ni1 and whose half-valuewidth was W_Ni1 was separated from the nickel total peak P_Ni. In FIG.28B, the thus obtained peak on nickel alone is indicated by the symbolP_Ni1.

Calculating Step of Peak Planar Dimension on Nickel Alone

Then, a planar dimension S_Ni1 of the peak P_Ni1 of nickel alone wascalculated. The planar dimension S_Ni1 is a planar dimension of an area(hatched area) surrounded by the peak P_Ni1 and the background lineBG_Ni in FIG. 28C.

In addition, a planar dimension of the nickel total peak P_Ni wascalculated. The planar dimension of the nickel total peak P_Ni is aplanar dimension of an area surrounded by the nickel total peak P_Ni andthe background line BG_Ni in FIG. 28C.

Then, a planar dimension S_Ni (REST) shown in FIG. 28C was calculated bysubtracting the planar dimension S_Ni1 of the peak P_Ni of nickel alonefrom the planar dimension of the nickel total peak P_Ni. The planardimension S_Ni (REST) as calculated above was used as the aforementionedA1, i.e., the sum of the peak planar dimension value of nickel oxide andthe peak planar dimension value of nickel hydroxide.

For the purpose of reference, FIG. 28D shows a result of separating thetotal peak P_Ni of nickel into the following four peaks, i.e., the peakthe peak P_Ni2, the peak P_Ni3 and the peak P_Ni4. As described above,the peak P_Ni1 is a peak on nickel alone. In addition, the peak P_Ni2,the peak P_Ni3 and the peak P_Ni4 are peaks on nickel oxide or peaks onnickel hydroxide.

When the nickel total peak P_Ni is separated into the plurality of peaksas shown in FIG. 28D, the aforementioned planar dimension S_Ni (REST)corresponds to a total sum of the peak planar dimensions except the peakP_Ni1 on nickel alone. Namely, the planar dimension S_Ni (REST)corresponds to the sum of the peak planar dimension of nickel hydroxideand the peak planar dimension value of nickel hydroxide.

The planar dimension S_Ni1 of the peak P_Ni1 on nickel alone issometimes referred to as a planar dimension value of the peak P4, andthe planar dimension S_Ni (REST) is sometimes referred to as a planardimension value of the peak P3.

4. Calculation of A1/A2

A1/A2 was calculated based on the A1 and A2 as calculated above.

Evaluation on Adhesion Property to Resist Pattern

The aforementioned elongated metal plate of the first winding body wascut out by using a shear into a range of 200×200 mm, so as to obtain afirst sample. Then, a dry film including a photosensitive layer having athickness of 10 μm was attached to a surface of the first sample so asto provide a resist film on the surface of the first sample. After that,the resist film was exposed such that a grid-like resist pattern havinga width w was formed, as shown in FIG. 23. The width w was set at 100μm. Then, the first sample was immersed into a developing solution, anda time up to which the resist pattern having the width of 100 μm peeledoff from the first sample was measured. As the developing solution, asolution having a concentration of 5.0 g/L of sodium carbonatemanufactured by Soda Ash Japan Co., Ltd. was used. A temperature of thedeveloping solution was set at 24° C.

In this example, when it took the resist pattern immersed in thedeveloping solution 15 minutes or more to peel off, it was evaluatedthat the adhesion property was satisfactory. On the other hand, when ittook the resist pattern immersed in the developing solution less than 15minutes to peel off, it was evaluated that the adhesion property wasunsatisfactory. In this example, it took the resist pattern 13 minutesto peel off from the first sample. Thus, it can be said that theadhesion property between the first winding body from which the firstspecimen was cut out and the resist pattern is unsatisfactory.

Whether the resist pattern peels off from the metal plate or not can bejudged based the fact whether the resist pattern has a curved portion ornot, when the resist pattern is seen along the normal direction of thefirst surface of the metal plate. This is because, in the developingsolution, a portion of the resist pattern, which peels off from themetal plate, floats to deform. FIG. 27 shows an example of a schematicdiagram of the metal plate and the resist pattern in which a portion ofthe grid-like resist pattern peels off from the metal plate in thedeveloping solution.

Second to Fourth Winding Bodies

Similarly to the first winding body, a second winding body to a fourthwinding body around which an elongated metal plate having a thickness of20 μm was wound were manufactured, by using a base metal made of an ironalloy containing 34 to 38 mass % of nickel, less than 0.1 mass % ofchrome, balancing iron and unavoidable impurities. Further, similarly tothe first winding body, the second winding body to the fourth windingbody were subjected to the composition analysis and the evaluation onadhesion property to the resist pattern. FIGS. 24(a) and 24(b), FIGS.25(a) and 25(b) and FIGS. 26(a) and 26(b) show the respective results ofspecimens cut out from the second winding body, the third winding bodyand the fourth winding body, which were analyzed by means of theaforementioned XPS apparatus.

Summary of Evaluation Results of First to Fourth Winding Bodies

Table 3 shows the peak planar dimension values of the aforementionedrespective peaks P1 to P4, which were obtained by analyzing thespecimens taken out from the elongated metal plates of the first windingbody to the fourth winding body. In addition, Table 3 shows thecalculated results of A1/A2, where A1 is a sum of a peak planardimension value of nickel oxide and a peak planar dimension value ofnickel hydroxide, and A2 is a sum of a peak planar dimension value ofiron oxide and a peak planar dimension value of iron hydroxide. As shownin Table 3, the first winding body and the second winding body did notsatisfy the aforementioned condition (1). On the other hand, the thirdwinding body and the fourth winding body satisfied the aforementionedcondition (1). For the purpose of reference, Table 4 shows thecompositions of the elongated metal plates of the first winding body tothe fourth winding body, which were calculated by the compositionanalysis using the XPS method.

TABLE 3 Peak P1 Peak P2 Peak P3 Peak P4 A1/A2 First Winding Body 22329.34481.8 9090.5 4748.9 0.41 Second Winding Body 45167.9 8984.6 20021.67849.8 0.44 Third Winding Body 36717.5 5195.9 8444.0 6138.4 0.23 ForthWinding Body 27134.2 3991.4 7948.8 4690.9 0.29

TABLE 4 Composition (at %) C N O Fe Ni First Winding Body 12.7 1.0 46.532.1 7.7 Second Winding Body 15.6 0.8 47.4 29.5 6.7 Third Winding Body32.7 0.8 40.4 22.2 4.0 Forth Winding Body 18.4 1.2 45.9 28.5 6.1Summary of Evaluation Results on Adhesion Property to Resist Pattern

Table 5 shows results of evaluation of the adhesion property to theresist pattern, which was performed to the samples cut out from theelongated metal plates of the first winding body to the fourth windingbody. In the column “Adhesion Property” of Table 5, “Satisfactory” meansthat it took the resist pattern immersed in the developing solution 15minutes or more to peel off from the resist pattern, and“Unsatisfactory” means that it took the resist pattern immersed in thedeveloping solution less than 15 minutes to peel off from the resistpattern.

TABLE 5 Adhesion Peeling Time Property First Winding Body 13Unsatisfactory Second Winding Body 14 Unsatisfactory Third Winding Body35 Satisfactory Forth Winding Body 33 Satisfactory

As shown in Table 3 and Table 5, the samples cut out from the thirdwinding body and the fourth winding body had a satisfactory adhesionproperty to the resist pattern. On the other hand, the samples cut outfrom the first winding body and the second winding body did not have asufficient adhesion property to the resist pattern. From these results,it can be said that it is effective that, in the surface of the metalplate, a ratio of nickel oxide and nickel hydroxide relative to ironoxide and iron hydroxide is decreased, to be more specific, theaforementioned A1/A2 is made less than 0.4, in order to ensure theadhesion property to the resist pattern.

Fifth to Ninth Winding Bodies

Similarly to the first winding body, a fifth to eighth winding bodyaround which an elongated metal plate having a thickness of 20 μm waswound, and a ninth winding body around which an elongated metal platehaving a thickness of 18 μm was wound were manufactured, by using a basemetal made of an iron alloy containing 34 to 38 mass % of nickel, lessthan 0.1 mass % of chrome, balancing iron and unavoidable impurities.Further, similarly to the first winding body, the fifth winding body tothe ninth winding body were subjected to the composition analysis andthe evaluation on adhesion property to the resist pattern.

Summary of Evaluation Results of First to Fourth Winding Bodies

Table 6 shows the peak planar dimension values of the aforementionedrespective peaks P1 to P4, which were obtained by analyzing thespecimens taken out from the elongated metal plates of the fifth windingbody to the ninth winding body. In addition, Table 6 shows thecalculated results of A1/A2. As shown in Table 6, the sixth winding bodydid not satisfy the aforementioned condition (1). On the other hand, thefifth winding body and the seventh winding body to the ninth windingbody satisfied the aforementioned condition (1). For the purpose ofreference, Table 7 shows compositions of the elongated metal plates ofthe fifth winding body to the ninth winding body, which were calculatedby the composition analysis using the XPS method.

TABLE 6 Peak P1 Peak P2 Peak P3 Peak P4 A1/A2 Fifth Winding Body 24528.33176.6 9165.0 4292.1 0.37 Sixth Winding Body 28969.1 5527.5 13102.15083.0 0.45 Seventh Winding Body 33256.9 1043.7 6615.7 2013.6 0.20Eighth Winding Body 30606.3 3739.6 8098.6 6506.4 0.26 Ninth Winding Body97247.0 6789.0 19847.0 12266.0 0.20

TABLE 7 Composition (at %) C N O Fe Ni Fifth Winding Body 16.2 1.0 45.130.6 7.1 Sixth Winding Body 33.3 2.1 41.6 18.4 4.7 Seventh Winding Body24.6 0.8 47.7 24.2 2.7 Eighth Winding Body 25.9 0.6 42.0 27.0 4.6 NinthWinding Body 34.6 1.3 42.6 17.4 4.1Summary of Evaluation Results on Adhesion Property to Resist Pattern

Table 8 shows results of evaluation of the adhesion property to theresist pattern, which was performed to the samples cut out from theelongated metal plates of the fifth winding body to the ninth windingbody.

TABLE 8 Adhesion Property Fifth Winding Body Satisfactory Sixth WindingBody Unsatisfactory Seventh Winding Body Satisfactory Eighth WindingBody Satisfactory Ninth Winding Body Satisfactory

As shown in Table 6 and Table 8, the samples cut out from the fifthwinding body and the seventh winding body to the ninth winding body hada satisfactory adhesion property to the resist pattern. On the otherhand, the sample cut out from the sixth winding body did not have asufficient adhesion property to the resist pattern. From these results,it can be said that it is effective that the aforementioned A1/A2 ismade less than 0.4, in order to ensure the adhesion property to theresist pattern. Namely, the aforementioned condition (1) is a powerfuljudgment method for selecting a metal plate.

DESCRIPTION OF SYMBOLS

-   20 Deposition mask-   21 Metal plate-   21 a First surface of metal plate-   21 b Second surface of metal plate-   22 Effective area-   23 Peripheral area-   25 Through-hole-   30 First recess-   31 Wall surface-   35 Second recess-   36 Wall surface-   43 Top portion-   64 Elongated metal plate-   64 a First surface of elongated metal plate-   64 b Second surface of elongated metal plate-   65 a First resist pattern-   65 b Second resist pattern-   65 c First resist film-   65 d Second resist film-   81 Irradiation unit-   82 Detection unit-   98 Deposition material

The invention claimed is:
 1. A metal plate used for manufacturing adeposition mask having a plurality of through-holes formed therein,wherein: when a composition analysis of a first surface of the metalplate is performed by using an X-ray photoelectron spectroscopy, a ratioA1/A2 obtained by the result of the X-ray photoelectron spectroscopy is0.4 or less, where A1 is a sum of a peak planar dimension value ofnickel oxide and a peak planar dimension value of nickel hydroxide, andA2 is a sum of a peak planar dimension value of iron oxide and a peakplanar dimension value of iron hydroxide; and in the compositionanalysis of the first surface of the metal plate by means of the X-rayphotoelectron spectroscopy, an incident angle of an X-ray emitted to themetal plate on the first surface is 45 degrees, and an acceptance angleof photoelectrons discharged from the metal plate is 90 degrees.
 2. Themetal plate according to claim 1, wherein a thickness of the metal plateis 85 μm or less.
 3. The metal plate according to claim 1, wherein athickness of the metal plate is 20 μm or less.
 4. The metal plateaccording to claim 1, wherein the metal plate is for manufacturing thedeposition mask by exposing and developing a dry film attached to thefirst surface of the metal plate to form a first resist pattern, and byetching an area of the first surface of the metal plate to form theplurality of through-holes, the area being not covered with the firstresist pattern.
 5. The metal plate according to claim 1, wherein theratio A1/A2 is 0.3 or less.
 6. A manufacturing method for a depositionmask having a plurality of through-holes formed therein, the methodcomprising: a step of preparing a metal plate; a first resist patternforming step of forming a first resist pattern on a first surface of themetal plate; and an etching step of etching an area of the first surfaceof the meal plate, the area being not covered with the first resistpattern, so that first recesses to define the through-holes are formedin the first surface of the metal plate; wherein: when a compositionanalysis of a first surface of the metal plate is performed by using anX-ray photoelectron spectroscopy, a ratio A1/A2 obtained by the resultof the X-ray photoelectron spectroscopy is 0.4 or less, where A1 is asum of a peak planar dimension value of nickel oxide and a peak planardimension value of nickel hydroxide, and A2 is a sum of a peak planardimension value of iron oxide and a peak planar dimension value of ironhydroxide; and in the composition analysis of the first surface of themetal plate by means of the X-ray photoelectron spectroscopy, anincident angle of an X-ray emitted to the metal plate on the firstsurface is 45 degrees, and an acceptance angle of photoelectronsdischarged from the metal plate is 90 degrees.
 7. The manufacturingmethod for a deposition mask according to claim 6, wherein a thicknessof the metal plate is 85 μm or less.
 8. The manufacturing method for adeposition mask according to claim 6, wherein a thickness of the metalplate is 20 μm or less.
 9. The manufacturing method for a depositionmask according to claim 6, wherein the first resist pattern forming stepincludes a step of attaching a dry film to the first surface of themetal plate, and a step of exposing and developing the dry film to formthe first resist pattern.
 10. The manufacturing method for a depositionmask according to claim 6, wherein the ratio A1/A2 is 0.3 or less.